Aromatic polyether amines



Patented Oct. 11, 1938 A UNITED STATES PATENT OFFICE.

Biihm a Haas Company. Philadelphia, Pa.

No Drawing. Application July 81, 1836,

7 Serial No. 03,571

15mins. (Cl. 260-574) This invention relates to condensation products oiprimary orsecondary aromatic amines with aryloxypolyalkylene etherhalides, said condensation products having the following formula:

R0A(OA).0-A-1!IB where R. signifles an aromatic group of the naphthaleneor benzene series, A is an alkylene radical 10 containing at least twocarbon atoms, n is one or zero, and X is hydrogen or an alkyl group.

Condensation products oi this type can readily be prepared by reactingprimary or secondary amines, such as aniline, the toluidines, thexylidines, the naphthylamines, diphenylamine, di-

naphthylamine, and N monoalkyl aromatic amines, such asN-methyl-aniline, N-methylnaphthylamines, with aryloxypolyalkylene etherhalides, such as those having the following formulae:

In applications Serial Nos. 82,183 and 82,184

filed May 28, 1936 I show the preparation of additionalaryloxypolyalkylene ether halides and their condensation with primary orsecondary aliphatic, cycioaliphatic, arylaliphatic and hydroxyaliphaticamines or secondary heterocyclic amines. I have now found thataryloxypolyalkylene ether halides of the above type also react witharomatic primary or secondary amines to form condensation products. Thereaction may be carried out by heating an equimolecular mixture of anaryloxypolyalkylene ether halide and an aromatic amine at from 100 to160 C. for approximately four to sixteen hours. Preferably an excess ofamine is. used and the reaction carried out under reflux or in a closedvessel at a temperature between 110 and 115 C. ior'i'rom eight tosixteen hours. An inert organic liquid may be used as a diluent,toluene, xylene or naphthalene being useful for this purpose. Aninorganic base such as the carbonate orhydroxide of an alkali or analkaline earth metal may be used to bind the hydrogenhalide termed.

In order to illustrate this invention, the following examples are given,the parts indicated being by weight.

Example 1 A mixture consisting of parts aniline and 43 parts ,3 phenoxyp chlorodiethyl ether was heated under a reflux condenser for eighthours at 110 C. while stirring. Crystals of the hydrochloride of thebase formed. The reaction mixture was then made alkaline with 100 partsof 10% caustic soda solution and heated for one-halt hour. The oil layerwhich separated was washed with water, dried, and fractionated underreduced pressure. The product, consisting offl-phenoxyp-phenylamino-diethyl ether, distilled over at 204 to 207 0/7mm. as a pale yellow oil. Yield 55-65% of theory.

By substituting 47 parts of p-phenoxy-p'- chlorodiisopropyl ether forthe 43 parts of phenoxy-fl'-chlorodiethyl ether in the foregoing examplean amine having the formula may be prepared.

Example 2 A mixture consisting of 70 parts aniline and 52 parts ofp-ter-octylphenoxyethoxyethyl chloride (a colorless oil, 13. P. 177 to178 0/4 mm., obtained by condensing p,p'-dichlorodiethyl ether with p-a,a,wy-tetramethylbutylphenol in the presence of caustic soda) was heatedunder a reflux condenser ior eight hours at to C. The reaction mixturewas made alkaline and worked up as in Example 1. The product boiled at250 to 255 C/6 mm. Yield 65-70% of theory.

Example 3 A mixture of 28.2 grams oi p-cyclohexylphenoxyethoxyethylchloride and 18.6 grams aniline was heated at to C. under reflux whileconstantly agitated for sixteen hours and worked up as in Example 1. TheN-p-cyclohexylphenoxyethoxyethyl aniline boiled at 271 to 2'13 C/li mm.Yield 28 grams. 1

Example 4 A mixture or 50.1 grams of p(p-naphthoxy) ethoxy-ethylchloride and 42.8 grams of orthotoluidine was heated for seven andone-half hours at 130 to 140 C. under reflux and worked up as inExample 1. The N-MB-naphthoxy) ethoxyethyl-o-toluidine boiled at 268 to271 C/5 mm. Yield 51 grams. .It formed a crystalline mass. M. P. 69 C.(from petroleum ether).

A mixture of 50 grams phenoxyethoxyethyl chlo- 'ride and 71.5 grams ofa-naphthylamine was heatmm. as a pale yellow oil.

ed at 140 to 145 C. for 20 hours under reflux, and worked up as inExample 1. The N-phenoxyethoxy-ethyl-a-naphthylamine boiled at 270 to280 C/6 mm. Yield 50 grams.

' Example 6 A mixture of 20.7 grams N-methyl aniline and 25.6 gramsp-ter-butylphenoxyethoxyethyl chloride was heated under reflux for eighthours at 130 to 140 C. The reaction mixture was boiled with 100 cc. of10% caustic soda solution for one hour, the oil taken up in ether, and180? tionated. The N-p-ter-butylphenoxyethorwethyl- N-methyl anilinecame over at 198 to 201 C/2 Yield 83% 01! theory.

Example 7 C/3 mm. as a pale yellow oil. Yield2'l grams.

A mixture consisting of 28.4 grams ofp-ter-butylphenoxy-isopropoxy-isopropyl chloride and 18.6 grams anilinewas heated eight hours at 130 to 140 C. and the reaction mixture madealkaline and worked up as in Example 1. The product distilled at 238 to244 C/4 mm. as a viscous, reddish oil.

Analogous reactions may be carried out with the following aromaticpolyether halides o! the type set forth herein, which are also disclosedin my copending applications Serial Nos. 82,188; 82,184 and 79.718, p'viously referred to, namely: (o-phenylphenoxy) ethyl-p'-chloroethylether p-(p-phenylphenoxy)ethyl-fl'-chloroethyl etherp-thymon-W-chloro-diethyl ether p-(1,3,5-xylenoxy) -p'-chloro-diethylether p-(p-ter-amylphenoxy) -p'-chlor o-diethyl ether(p-ter-butylphenonethoxy) -p'-chloro-dietbylether p-(:gter-amylphenoxyethoxy) -'p-chlorodiethyl e er p- (pnitrophenoxyethoxy) p chloro diethyl ether p-(o-benzylphenoxyethoxy) Bchloro diethyl ether ,8- (p-cresyloxyethoxy) -p'-chloro-diethyl ether.

In addition to the foregoing specific compounds other aryloxy polyetherhalides may be used, such as may be prepared from various phenols andvarious dihalogeno polyalkylene ethers as set forth in my co-pendingapplication Ser. No. 82,- 183 above referred to. Among the phenolssuitable for this purpose are phenol, 0-, m-, or pcresol, thymol,carvacrol, p-ter. butyl phenol, psec. butyl phenol, p-ter. amyl phenol,p-n-amyl phenol, n-amyl-m-cresol, p-sec. octyl phenol, pter. octylphenol, p-sec. hexyl phenol, lauryl phenol, o-, m-, or p-benzyl phenol,aor p-naphthol, ter. butyl-p-naphthol, ter. octyl-p-naphthol', 1,3,5-xylenol and their obvious equivalents. Among the dihalogeno polyalkyleneethers' suitable for condensation with the above-listed phenols are-p'-dichlorodiethyl ether, p-p-dichlorodiisopropyl ether,dichlorodibutyl ether, dichlorodiamyl ether and the correspondingdibromo derivatives, p-chloroethyl-p'-chloroethoxy ethyl ether and theirhigher homologs containing up to 18 carbon atoms.

The compounds made according to the present invention may be added torubber, lubricating oils and other autooxidizable materials in order toretard oxidation.

I claim: 1. An aromatic amine having the formula on, I cm careers-(nroriho-omcm-nn-cm.

2. An aromatic amine having the formula."

3. An aromatic amine having the formula CsHr0CHrCH 0-CHCH:NHCH| H: H:

4. An aromatic amine having the general I0l-' mula CsHKO OKs-CH1) .OCHaCHz-Ih-C '11;

mula in which'R is an aromatic hydrocarbonradical containing a nuclearsubstituent which is one of the group consisting of alkyl, aralkyl, andcycloallcyl radicals, R1 is an aromatic hydrocarbon radical, n is aninteger less than three, and X is a member of the group consisting ofhydrogen,

' lower alkyl groups and aryl groups.

9. An aromatic amine having the general forin which A represents loweralkylene radicals containing at least two carbon atoms, R is ahydrocarbon radical containing a nuclear substituent which is a memberof the group consisting of alkyl, aralkyl and cycloalkyl radicals, R1 isan aromatic hydrocarbon radical, n is an integer less than three, and Xis a member of the group consisting of hydrogen, lower allgvl groups andaryl groups. 1 c I 10. An aromatic amine having the general for- R 'inwhich A represents lower alkylene radicals containing at least twocarbon atoms, R. and R1 are aromatic hydrocarbon radicals, 11. is aninteger less than three, and X is a member of the group I consisting ofhydrogen, lower alkyl groups and aryl groups.

11. A condensation product of an amine having the general formula inwhich R1 is an aromatic radical and x is a member of the groupconsisting 01' hydrogen, lower alkyl groups and aryl" groups, with anaryloxy polyalkylene ether halide 01' the general formula Rr-(O-A)g-O-AY aromatic in which R is an aromatic hydrocarbon radical containinga nuclear substituent which is one of the group consisting of alkyl,aralkyl, and cycloalkyl radicals, A represents lower alkylene radicalscontaining more than two carbon atoms, n

is an integer less than three and Y is a halogen atom.

12. The process which comprises condensing an aromatic amine of thegeneral formula in which R1 is an aromatic radical and X is a member ofthe group consisting of hydrogen, lower alkyl groups and aryl groups,with an aryloxy polyalkylene ether halide of the general formula i 4inwhich R is an aromatic hydrocarbon radical containing a nuclearsubstituent which is one of the group consisting of alkyl, aralkyl andcycloalkyl radicals, A represents lower alkylene radi- 'cals containingmore than two carbon atoms, n

is an integer less than three and Y is a halogen atom.

13. An aromatic amine having the general formula a in which R is anaryloxy polyalkylene ether radical in which the alkylene groups areselected from the lower members of the series, R1 is an aromatichydrocarbon radical and X is a member of the group consisting ofhydrogen, lower alkyl radicals and aryl radicals.

14. An aromatic amine having the general forin which R is an aryloxypolyethylene ether radical, R1 is an aromatic hydrocarbon radical and Xis a member of the group consisting of hydrogen, lower alkyl radicalsand aryl radicals.

15. An aromatic amine having the general formula,

in which R is an aryloxy triethylene diether radical, R1 is an aromatichydrocarbon radical and X is a member of the group consisting ofhydrogen, lower alkyl radicals and aryl radicals.

HERMAN A. BRUSON.

